WO2017080473A1 - Membrane tubulaire de fibres ultrafines de polytétrafluoroéthylène - Google Patents

Membrane tubulaire de fibres ultrafines de polytétrafluoroéthylène Download PDF

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Publication number
WO2017080473A1
WO2017080473A1 PCT/CN2016/105274 CN2016105274W WO2017080473A1 WO 2017080473 A1 WO2017080473 A1 WO 2017080473A1 CN 2016105274 W CN2016105274 W CN 2016105274W WO 2017080473 A1 WO2017080473 A1 WO 2017080473A1
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WO
WIPO (PCT)
Prior art keywords
cavity
mass
fiber membrane
porous material
polytetrafluoroethylene
Prior art date
Application number
PCT/CN2016/105274
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English (en)
Chinese (zh)
Inventor
叶雷
Original Assignee
重庆润泽医药有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 重庆润泽医药有限公司 filed Critical 重庆润泽医药有限公司
Publication of WO2017080473A1 publication Critical patent/WO2017080473A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/364—Membrane distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes

Definitions

  • the present invention relates to a porous material, in particular a polytetrafluoroethylene fiber membrane, which is particularly suitable for membrane distillation.
  • porous material A solid containing a certain number of pores is called a porous material and is a material that forms a network structure by through or closed pores.
  • porous materials Compared with continuous medium materials, porous materials generally have the advantages of low relative density, high specific strength, high specific surface area, light weight, sound insulation, heat insulation and good permeability.
  • the porous material can be divided into microporous (pore size less than 2 nm) material, mesoporous (pore size 2-50 nm) material and macroporous (pore size greater than 50 nm) material.
  • Porous materials are classified according to their materials and can be classified into metal porous materials and non-metallic porous materials.
  • Non-metallic porous materials generally have the characteristics of large specific surface area, small density, small thermal conductivity, small relative density, and high porosity. They are used in catalysts (including carriers), adsorbents, heat preservation, heat insulation, sewage and waste gas treatment, filtration of liquids, and Gas (even bacteria), lightweight building materials, environmental protection, soil improvement, chemical industry and other fields have broad application prospects.
  • the polytetrafluoroethylene porous membrane material has a wide application range due to its temperature stability, chemical stability, electrical insulation, flame retardancy and self-lubricating properties. However, due to the randomness and irregularity of the pore structure, it still cannot satisfy many application properties.
  • the porous material itself needs to be uniform, its pore size and pore distribution are uniform, so that the performance is uniform, but in fact, many porous materials do not meet this requirement, and their uniformity complements; although some materials claim to be self-proclaimed Achieve higher uniformity, but its uniformity is still uniformity on a large volume scale. If it is measured by a small volume scale, for example, if a plurality of three-dimensional bodies having a volume of not more than one cubic centimeter are taken on the material, respectively, The quality, the degree of uniformity is still very large, thus causing various properties of the polytetrafluoroethylene porous membrane material such as strength, elastic modulus, flux and the like, which seriously affect its function.
  • the object of the present invention is to provide a polytetrafluoroethylene fiber membrane which is structurally suitable, controllable and highly uniform.
  • the object of the invention is achieved by the following measures:
  • a polytetrafluoroethylene ultrafine fiber membrane comprising a body of polytetrafluoroethylene material, a polytetrafluoroethylene fiber, a fiber diameter of 30-200 nm, a body having a pore size of 10 nm to 1000 nm, and a three-dimensional space surrounding the cavity
  • the cavity wall is formed with uniform distribution, and each cavity is three-dimensionally penetrated.
  • the uniform distribution of the cavity means that each cavity is uniformly distributed under arbitrary unit volume on the porous material; porosity is ⁇ 75%
  • the tensile strength is 15 N/mm 2 or more, and the water pressure resistance is 3 kg/cm 2 or more.
  • the polytetrafluoroethylene fiber membrane has a cavity having a pore diameter of 30 to 1000 nm and a cavity wall formed in a three-dimensional space around the cavity, and a lower cavity of 10 to 100 nm is disposed on the cavity wall, and each cavity of each cavity is three-dimensionally Through and holes
  • the cavities are also connected to each other; the cavities are uniformly distributed, and the uniformity of the cavities means that the cavities are uniformly distributed under arbitrary unit volume on the porous material.
  • the above unit-level volume means a cubic centimeter-level or cubic millimeter-level or smaller unit-level volume.
  • the uniform distribution of the above-mentioned cavities means that each of the three-dimensional bodies having a volume of not more than one cubic centimeter and the same size on the porous material is substantially equivalent in mass.
  • the above-mentioned mass is substantially equivalent to a plurality of three-dimensional bodies having a volume of not more than one cubic centimeter and the same size, which are respectively referred to as a mass, and an average value of their masses is obtained, and any three-dimensional mass is relatively
  • the absolute value of the deviation from the mass average is not more than 4% of the average of the three-dimensional body mass.
  • the three-dimensional bodies of the same size having a volume of not more than one cubic millimeter on the multi-stage material are substantially equivalent in mass.
  • the mass is substantially equivalent to a plurality of three-dimensional bodies of the same size having a volume of not more than one cubic millimeter on the porous material, respectively referred to as masses, and an average value of their masses is obtained, and any three-dimensional mass is obtained.
  • the absolute value of the deviation from the mass average is not more than 4% of the average of the three-dimensional body mass.
  • the polytetrafluoroethylene fiber membrane is composed of a multi-stage porous material
  • the body is a cavity which is classified by a material pore size, and a cavity wall which surrounds the cavity in a three-dimensional space, and a lower cavity is arranged on the cavity wall, and each The stages of the cavities are each three-dimensionally penetrated and the cavities of the stages are also connected to each other.
  • the next level of porous material constitutes the wall of the cavity of the upper stage.
  • the cavity wall of the upper cavity is composed of a multi-stage porous material of its lower stage or a composite of porous materials of the lower stage, so that the material can meet specific functional requirements.
  • each stage of the porous material of the material body is self-contained as a continuous structure.
  • the maximum outer boundary of each level of porous material is comparable to the entire material body space boundary. That is, each grade of porous material can exist in the bulk as a first-order independent porous material, and has its own physical and chemical properties. Such a structure can make the physical and chemical properties of the porous materials of different levels different, and have different physical and chemical properties in the entire space of the relatively fixed materials, and better meet various functional requirements.
  • the present invention provides a polytetrafluoroethylene fiber membrane having a porous structure, and the structural form thereof is clarified, and the hierarchical structure of the pore cavity and the uniform structure thereof can satisfy various functional requirements.
  • the present invention provides a specific and clear measurement method for the uniform distribution of the pores of the polytetrafluoroethylene fiber membrane, and clarifies that the pore distribution uniformity of the porous material and its multi-stage structure is measured on the scale of the small unit volume.
  • Such a porous structure is highly uniform, thereby ensuring uniformity of the properties of the porous material.
  • the polytetrafluoroethylene fiber membrane of the present invention is three-dimensionally penetrated, including three-dimensional communication of each level of holes, and three-dimensional through-holes of each level, and good penetration, and can fully meet the functional requirements of the material.
  • the polytetrafluoroethylene fiber membrane of the present invention is a hydrophobic surface having a multistage roughness structure.
  • the surface water contact angle can reach 160° or more.
  • Polytetrafluoroethylene porous fiber membrane such as pore distribution, hierarchical structure, porosity, pore shape and other structural characteristics, processes and the like are related to mechanical properties such as mechanical strength and water pressure resistance, and the polytetrafluoroethylene fiber membrane of the present invention No support, stable shape, controllable thickness, applied to membrane distillation process, flux >42L/m 2 ⁇ h, rejection rate above 99.8%, tensile strength up to 30N/mm 2 or more, water pressure resistance 5kg/cm 2 the above.
  • the polytetrafluoroethylene fiber membrane of the present invention may be a film of different shapes and specifications such as a flat plate type, a tubular type, a hollow fiber type or a roll type, without support, and has a stable shape and a controllable thickness.
  • the polytetrafluoroethylene fiber membrane of the invention has a secondary pore structure, wherein the cavity wall of the first-stage cavity uniformly distributed and interpenetrating has a second-stage cavity uniformly distributed and mutually penetrating, and the two-stage hole The two are also connected to each other, and the through-holes are three-dimensionally penetrated.
  • Each level of porous material of the material body is self-contained as a continuous structure.
  • the total effective porosity is 75%
  • the fiber diameter is 150 ⁇ 20 nm
  • the macroporous average pore diameter is 0.45 ⁇ m
  • the preparation method of the polytetrafluoroethylene porous material is:
  • a polytetrafluoroethylene emulsion having a solid content of 60%, a chitosan having a particle size of 30 nm, a 5% (mass ratio) polyacrylic acid solution, and a 20 wt% starch emulsion are uniformly mixed according to the mass of 50:25:4:4. Ratio, formulated into a spinning solution;
  • the precursor film is wound up to 5 layers on a cylindrical support mold, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and sintering is sequentially sintered by program temperature control, and is heated from room temperature at a rate of 5 ° C/min.
  • Incubate at 160 ° C for 80 min at 160 ° C; ramp up to 280 ° C at 5 ° C / min, hold at 280 ° C for 60 min; ramp to 360 ° C at 2 ° C / min, hold at 360 ° C for 20 min; at 6 ° C /
  • the rate of min was raised to 400 ° C and incubated at 400 ° C for 60 min.
  • the PTFE fiber membrane does not need to be supported, has stable shape and controllable thickness, and can be used for gas-liquid separation and liquid-liquid separation to achieve precise grading filtration, for example, it is suitable for filtering of two-component or multi-component gas (liquid) body,
  • the flux is large, the rejection rate is high, and it is not easy to be polluted (such as the contamination of the multi-liquid immersion membrane), and has the advantages of high efficiency and long-term efficiency.
  • the film water contact angle was 168°; the tensile strength was 30 N/mm 2 , and the water pressure resistance was 5 kg/cm 2 .
  • Volatile alcohol/acid separation factor [alcohol / acid mass fraction in distillate ⁇ (1 - raw material liquid alcohol / acid mass fraction)] ⁇ [raw material liquid alcohol / acid mass fraction ⁇ (1- distillate alcohol / acid mass fraction)] can reach 10 the above.
  • the polytetrafluoroethylene fiber membrane of the invention has a three-stage pore structure, wherein the cavity wall of the first-stage cavity uniformly distributed and interpenetrating has a second-stage cavity uniformly distributed and mutually penetrating, and the two-stage hole The two are also connected to each other, and the through-holes are three-dimensionally penetrated.
  • Each level of porous material of the material body is self-contained as a continuous structure.
  • the total effective porosity is 85%, the fiber diameter is 180 ⁇ 20 nm, the macroporous average pore diameter is 800 nm, and there are average secondary pores of 60 nm in the cavity wall of the macropores, and there is an average on the pore walls of the second-stage pores.
  • a third-stage hole having a pore diameter of 10 nm.
  • the preparation method of the polytetrafluoroethylene porous material is:
  • the precursor film is wound up to 5 layers to a 2 mm diameter cylindrical support mold, sent to a tube furnace for sintering in a vacuum or a protective atmosphere, and sintered by program temperature control and continuous sintering at a rate of 5 ° C / min.
  • the temperature is raised to 160 ° C at room temperature, 80 min at 160 ° C; the temperature is raised to 290 ° C at 5 ° C / min, incubated at 290 ° C for 60 min; the temperature is raised to 360 ° C at 2 ° C / min, and kept at 360 ° C for 20 min;
  • the rate of °C/min is raised to 400 ° C, and kept at 400 ° C for 60 min;
  • the program was temperature-controlled and cooled, and a porous polytetrafluoroethylene hollow fiber membrane having a three-stage pore structure was obtained according to a conventional technique, and the thickness was 168 ⁇ m, and the fiber membrane diameter was 2 mm.
  • the PTFE fiber membrane does not need to be supported, has stable shape and controllable thickness, and can be used for gas-liquid separation and liquid-liquid separation to achieve precise grading filtration, for example, it is suitable for filtering of two-component or multi-component gas (liquid) body,
  • the flux is large, the rejection rate is high, and it is not easy to be polluted (such as the contamination of the multi-liquid immersion membrane), and has the advantages of high efficiency and long-term efficiency.
  • the film water contact angle was 170°; the tensile strength was 28 N/mm 2 , and the water pressure resistance was 7 kg/cm 2 .
  • Alcohol/acid separation factor [alcohol/acid mass fraction in distillate ⁇ (1 - raw material liquid ethanol mass fraction)] ⁇ [raw material liquid alcohol / acid mass fraction ⁇ (1-distillate alcohol / acid mass fraction)] Can reach more than 10.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Artificial Filaments (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne une membrane tubulaire de fibres ultrafines de polytétrafluoroéthylène comprenant un corps de matériau de polytétrafluoroéthylène; le polytétrafluoroéthylène a une forme de fibre et la fibre a un diamètre de 30 à 200 nm; le corps comporte des cavités de pore ayant un diamètre de 10 à 1000 nm et des parois de cavité formées par des espaces tridimensionnels entourant les cavités de pore; les cavités de pore sont uniformément distribuées et chaque cavité de pore est ouverte de façon tridimensionnelle; la porosité est ≥ 75 %, la résistance à la traction est de 15 N/mm² ou plus, et la résistance à la pression d'eau est supérieure à 3 kg/cm² ou plus.
PCT/CN2016/105274 2015-11-11 2016-11-10 Membrane tubulaire de fibres ultrafines de polytétrafluoroéthylène WO2017080473A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510767099.2 2015-11-11
CN201510767099.2A CN106669457B (zh) 2015-11-11 2015-11-11 一种聚四氟乙烯超细纤维膜

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WO2017080473A1 true WO2017080473A1 (fr) 2017-05-18

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109550401A (zh) * 2017-09-26 2019-04-02 重庆润泽医药有限公司 一种膜蒸馏用复合材料

Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101530750A (zh) * 2009-04-20 2009-09-16 浙江理工大学 聚四氟乙烯超细纤维多孔膜的制备方法
CN101543734A (zh) * 2008-11-21 2009-09-30 任正善 一种聚四氟乙烯纳米纤维膜及制备方法
CN102151493A (zh) * 2011-03-18 2011-08-17 上腾新材料科技（苏州）有限公司 一种纳米级聚四氟乙烯微孔膜的制备方法
WO2013005430A1 (fr) * 2011-07-05 2013-01-10 日東電工株式会社 Film poreux de polytétrafluoroéthylène et matériau filtrant pour filtre à air
CN103191653A (zh) * 2012-01-10 2013-07-10 杭州科百特过滤器材有限公司 一种形成非对称聚四氟乙烯多孔膜的方法

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JP4659241B2 (ja) * 2001-03-19 2011-03-30 ジャパンゴアテックス株式会社 ポリテトラフルオロエチレン膜及びその製造方法
CN102941025A (zh) * 2012-11-20 2013-02-27 浙江理工大学 一种膜蒸馏用聚四氟乙烯中空纤维膜的制备方法
CN107537327B (zh) * 2014-03-13 2020-01-03 成都百途医药科技有限公司 一种聚四氟乙烯膜及其制备方法
CN103894077B (zh) * 2014-04-10 2016-02-24 江南大学 一种多维度孔隙结构复合过滤膜及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101543734A (zh) * 2008-11-21 2009-09-30 任正善 一种聚四氟乙烯纳米纤维膜及制备方法
CN101530750A (zh) * 2009-04-20 2009-09-16 浙江理工大学 聚四氟乙烯超细纤维多孔膜的制备方法
CN102151493A (zh) * 2011-03-18 2011-08-17 上腾新材料科技（苏州）有限公司 一种纳米级聚四氟乙烯微孔膜的制备方法
WO2013005430A1 (fr) * 2011-07-05 2013-01-10 日東電工株式会社 Film poreux de polytétrafluoroéthylène et matériau filtrant pour filtre à air
CN103191653A (zh) * 2012-01-10 2013-07-10 杭州科百特过滤器材有限公司 一种形成非对称聚四氟乙烯多孔膜的方法

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CN106669457B (zh) 2020-11-20
CN106669457A (zh) 2017-05-17

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